2-substituted benz-x-azol-6-yl-2h-naphtho(1,2-d)triazoles

ABSTRACT

2-BENZOXAZOL-6-YL-2H-NAPHTHO(1,2-D)TRIAZOLES, 2-BENZOTHIAZOL-6-YL-2H-NAPHTHO(1,2-D)TRIAZOLES AND 2-BENZIMIDAZOL-6-YL-2H-NAPHTHO(1,2-D)TRIAZOLES, HAVING ATTACHED AT THE 2-POSITION OF THE BENZ-X-AZOL-6-YL RING THEREOF A SUBSTITUENT OF FROM 8-18 CARBON ATOMS AND 4-8 CONJUGATED DOUBLE BONDS, ARE OPTICAL WHITENING AND BRIGHTENING AGENTS HAVING PARTICULARLY DESIRABLE SHADES OF FLUORESCENCE.

United States Patent US. Cl. 260-240 D Claims ABSTRACT OF THE DISCLOSURE2-benzoxazol-6-yl-2H-naphtho[1,2-d1triazoles,2-benzothiazol-6-y1-2H-naphtho[1,2-d1triazoles and2-benzimidazol-6-yl-2H-naphtho[1,2-d]triazoles, having attached at the2-position of the benz-X-azol-6-yl ring thereof a substituent of from8-18 carbon atoms and 4-8 conjugated double bonds, are optical whiteningand brightening agents having particularly desirable shades offluorescence.

This application is a continuation-in-part of my prior copending US.patent application Ser. No. 46,482, filed June 15, 1970, now US. Pat.No. 3,689,425, issued Sept. 5, 1972, which in turn is acontinuation-in-part of my copending US. patent application Ser. No.655,339, filed July 24, 1967, now US. Pat. 3,575,956, issued Apr. 20,1971.

This invention relates to novel fluorescent compounds of thenaphthotriazole type useful as whitening and brightening agents and tothe preparation thereof.

The present invention provides new fluorescent whitening and brighteningagents which are useful in the treatment of threads, sheets, films,filaments, textile fabrics and the like, as well as in the manufactureof paper, varnishes, inks, coatings and plastics. In particular, myinvention provides whitening and brightening agents of thenaphthotriazole series which have a pleasing shade of fluorescence andhave good stability to light and to chlorine-type bleaches.

The novel compounds of my invention are 2I-I-naphtho- [1,2-d]triazolesbearing in the 2-position thereof a benz- X-azol-6-yl radical, in turnhaving a substituent in the 2-position thereof which is an organicradical of about eight to eighteen carbon atoms and having from four toeight conjugated double bonds, from zero to two of which areincorporated into an acyclic bridge, wherein X is O, S or NR. Thebenz-X-azol-6-yl radical is a member ,selected from the class consistingof benzoxazol-6-yl, benzothiazol-6-yl, and benzimidazol-6-yl radicals.The 2H- naphtho[l,2-d]triazole portion of the structure of my newcompounds is either unsubstituted or bears water solubilizing groups ofthe carboxylic or sulfo class.

The compounds of my invention are depicted structurally as shown inFormula I,

3 4 /N a-1% X/1 ll 1 N 9 wherein X is a member of the class consistingof O, S, and NR, where R is a member of the class consisting ice of H,lower alkyl, hydroxy-lower alkyl, hydroxy-oxaalkyl, phenyl-lower alkyl,cyano-lower alkyl, carboxy-lower alkyl, carbalkoxy-lower alkyl,phenyl-hydroxy-lower alkyl, and lower alkenyl; Y is an organic radicalof from eight to eighteen carbon atoms containing from four to eightconjugated double bonds, from zero to two of which are incorporated intoan acyclic bridge; and Z is a member of the class consisting of H, fromone to two carboxy, and from one to two sulfo groups.

The compounds of Formula I, in which as above indicated the substituentY contains at least four conjugated double bonds, have a desirable blueshade of fluorescence. This is in contrast with the properties of thecorresponding compounds wherein Y contains less than four conjugateddouble bonds, which have a poor shade of fluorescence, i.e., they appearred or reddish-violet under the influence of ultraviolet light, and onthe other hand is in contrast with the properties of the correspondingcompounds wherein the number of conjugated double bonds in thesubstituent Y exceeds eight, in which the fluorescence tends to be tooyellow for the resulting compounds to be useful as whitening andbrightening agents according to present standards.

I have also found that compounds of Formula I wherein Y contains morethan eight conjugated double bonds tend to absorb light in the visibleregion of the spectrum and thus appear colored. These compounds aregenerally unacceptable as whitening and brightening agents. Hence Iconsider the range of four to eight conjugated double bonds in the Ysubstituent to be a critical feature of my invention. The Y function inFormula I may be varied widely within the definition set forth above toprovide species within the ambit of my invention.

Preferred groups represented by the term Y are those having thestructure wherein A is a cyclic aromatic radical containing from four toseven internally conjugated double bonds and m is an integer having avalue of 0-2 such that the sum of m and the number of conjugated doublebonds in the cyclic aromatic radical A falls within the range four toeight.

Among those groups represented by the substituent Y which are consideredof particular value for the purposes of my invention are styryl, 5phenyl 2 furyl, 2- quinolinyl, 3-coumarinyl, Z-naphthyl, 2-benzofuranyl,2 (6 methylbenzofuranyl) 2 dibenzofuranyl, 3 dibenzofuranyl, p (3coumarinyl)phenylene, 2 benzoxazolyl, 2 (benzoxazol 2 yl)vinyl, 2 (2benzimidazolyl)- vinyl, 4-stilbyl, 4-(2-furyl) 1,3 butadienyl,3-indolyl, 2 indenyl, 9 phenanthryl, 9 fluorenyl, 2-quinoxalinyl, 4 (2thienyl) 1,3 butadienyl, 2 (2 pyridyl)vinyl, 2 (4 pyridyl)vinyl,4-methylstyryl, 2-(2-naphthyl)- vinyl, 2 (l naphthyl)vinyl, 4 phenyl 1,3butadienyl, 2-(4-biphenylyl)-vinyl, and the like.

In Formula I, X is O, S, or NR. When X is NR, the R is a radical of theclass consisting of H; lower alkyl, preferably containing from one tosix carbon atoms, for example, methyl, ethyl, isopropyl, n-propyl,n-butyl, isobutyl, and n-hexyl; hydroxy-lower alkyl, preferablycontaining from two to six carbon atoms, for example, hydroxyethyl, 2hydroxypropyl, and 2,3 dihydroxypropyl; hydroxy-oxaalkyl, preferablycontaining from three to fifteen carbon atoms, for example 2-hydroxy 3(2,3- dihydroxypropoxy)propyl, 2 hydroxy 3 (Z-hydroxyethoxy)propyl, and2 hydroxy 3 [2 (2 hydroxyethoxy)ethoxy]propyl; phenyl-lower alkyl,preferably containing from seven to eleven carbon atoms, for examplebenzyl, phenethyl, 3 phenylpropyl and 3 phenylpentyl; cyano-lower alkyl,preferably containing from three to six carbon atoms, for example, 2cyanoethyl, 3-cyanopropyl and 4-cyanopentyl; carboxyl-lower alkyl,preferably containing from two to six carbon atoms, for example,carboxymethyl, 2 carboxyethyl, 3 carboxypropyl and S-carboxypentyl;carbo-lower alkoxy-lower alkyl, preferably containing a total of fromthree to twelve carbon atoms, for example, carbomethoxymethyl 2carbomethoxyethyl, 2 carbobutoxyethyl, 3 carbohexyloxypropyl andS-carbomethoxypentyl; phenyl-hydroxy-lower alkyl, preferably containingfrom eight to eleven carbon atoms, for example p-phenyl B hydroxyethyl,a-phenyl-phydroxyphenyl, and fl-phenyl-B-hydroxpropyl; and lower alkenylpreferably containing from 3 to 6 carbon atoms, for example, allyl,methallyl, and 3,3-dimethallyl.

In Formula I, Z is H, one or two carboxy, or one or two sulfosubstituents. As indicated by the bond in Formula I, which is notdirected to any specific position, where Z is carboxy or sulfo, it maybe attached at any of the six available positions on thenaphtho[1,2-d]triazole ring, and when more than one such substituent ispresent, they may be in any of the several positions related to eachother. Where Z is carboxy or sulfo, its presence is for the purpose ofimparting water solubility and/or dispersibility to the resultingcompound through salt formation. Thus, the commonly-used alkali metaland quaternary ammonium salts of said compounds are the full equivalentsof the corresponding free acids herein claimed.

In general, the compounds of Formula I are high-melting tan to yellowsolids. The compounds wherein Z is hydrogen are insoluble in water, thelower alcohols, ketones and mineral acids, and they are moderatelysoluble in dimethylformamide and high-boiling, non-polar aromatichydrocarbons. The compounds wherein Z is carboxy or sulfo, in their freeacid form, are substantially insoluble in water and are moderatelysoluble in dimethylformamide, dimethylsulfoxide and acetic acid, and inthe form of their alkali metal or quaternary ammonium salts, have lowsolubility in water and are generally moderately soluble in2-ethoxyethanol and dimethylformamide.

When the compounds of the present invention are dispersed or dissolvedin aqueous media, they fiuoresce bluewhite under ultraviolet light.Those compounds having carboxy or sulfo substituents are particularlysubstantive to a wide variety of natural and synthetic fibers, forexample cotton, cellulose acetate, viscose rayon and nylon, and areabsorbed by such fibers from very low concentrations in aqueousdispersions. Those compounds having no carboxy or sulfo substituents areparticularly adapted to incorporation into plastic and synthetic fibermelts and to application to fabrics by the known heat-settingprocedures. The compounds of the invention also have high stability tosunlight, soap, synthetic detergents and chlorine-type bleaches.

The above-described properties of my new compounds make them especiallyvaluable as whitening and brightening agents in treating white andcolored fabrics in order to neutralize the yellowness which develops inwhite textiles and to enhance the brilliance of colored textiles. Insuch utilization the high resistance of my compounds to ch10 rinebleaches and to light are distinct advantages. A further importantadvantage of the compounds of my invention lies in their property ofbuilding up the amount of whitening agent on the fibers of textiles onrepeated application of the whitening agent without developing anundesirable discoloration, for example a reddish or grey color, such asis produced by many of the known optical bleaching agents when they areapplied repeatedly, as in successive launderings.

The compounds of my invention are conveniently prepared by diazotizing a6-aminobenz-X-azole appropriately substituted in the 2-position thereofby substituent Y, then coupling the diazonium salt thus formed to eithera l-aminonaphthalene which is substituted in the 4-position or aZ-aminonaphthalene which is either unsubstituted or substituted with oneor two carboxy groups or one or two sulfo groups, as desired, and thenoxidizing the resulting ortho-amino azo compound according to known 4methods to give the desired 2 substituted -2H-naphtho [l,2-d]triazole ofFormula I.

Diazotization of the intermediate 6-aminobenz- -azole compounds isreadily carried out by methods well known in the art, for example bydissolving the amine in an excess of mineral acid, for example bydissolving the amine in an excess of mineral acid, for example,hydrochloric acid, in ice and adding a molecular equivalent of sodiumnitrite. Where the 6-aminobenz-X-azole or the resulting diazonium saltis only slightly soluble in aqueous mineral acid, the addition of aceticacid or dimethylformamide generally helps to keep the material insolution.

The coupling reaction is preferably carried out in acid medium at roomtemperature, whereby said diazonium compound is coupled to anaminonaphthalene adapted for coupling in a position ortho to the aminogroup. This condition implies that the amino group is located inposition 2 of the naphthalene ring, and that position 1 isunsubstituted; or that the amino group is located in position 1 of thenaphthalene ring, that position 2 is unsubstituted, and also thatposition 4 is blocked by a carboxy or sulfo group in order that couplingwill not occur in the 4-position, that is, para to the amino group. Whenthe coupling reaction is complete, I prefer to heat the reaction mixtureto about C. for several hours to increase the crystal size of theresulting pigment.

The resulting ortho-amino-azo compound is converted to the desiredtriazole compound by oxidation procedures well known in the art. Forexample, the ortho-aminoazo compound is heated in an aqueous solution ofcupric sulfate containing an excess of an amine, for example ammoniumhydroxide or pyridine, or alternatively, in an aqueous alkaline solutionof sodium hypochlorite. Oxidation to the desired naphthotriazole iscomplete when the deep color of the intermediate azo dye hasdisappeared. The product is conveniently isolated from the reactionmixture by pouring the latter into an excess of mineral acid (forexample hydrochloric acid or sulfuric acid) in ice, and collecting the2-substituted-2H- naphtho[1,2-d]triazole of Formula I whichprecipitates. The products are purified by recrystallization fromorganic solvents in the usual manner.

Those compounds of Formula I wherein X is NI-I are convenientlyalkylated according to procedures known in the art. For example, US.Pat. 2,838,504 presents a full disclosure of methods for alkylation ofthe benzimidazole ring which are applicable here; and in particular,those procedures are useful for substituting in the benzimidazole ringin the 1-position the following groups: lower alkyl, hydroxy-loweralkyl, 2-hydroxy-3-sulfopropyl, hydroxy-oxaalkyl, carboxyl-lower alkyl,cyano-lower alkyl, monocyclic aralkyl, and lower alkenyl.

For incorporation into synthetic plastic materials, I particularlyprefer those compounds of Formula I bearing no water solubilizing groupson the 2H-naphtho[1,2- d]triazole ring, i.e., compounds having thestructure of Formula II Formula II wherein X and Y have the samemeanings indicated hereinabove. These preferred species have been foundto have high stability to heat and light in addition to the otheradvantageous properties common to all my new compounds as set forthabove.

A preferred mode of utilizing the compounds of Formula II is toincorporate them into melts of synthetic plastic material for spinningsynthetic fibers or for casting or molding plastics in an appropriateconcentration, for example 0.01 to 0.1 percent by weight of the melt.

A further method of utilizing the compounds of Formula II is toimpregnate textile fabrics comprising synthetic fibers, for examplepolyester (poly[terephthalic acid ethylene glycol ester]) or nylon, withan aqueous dispersion of the compound at temperatures below about 75 C.,for example, at room temperature and then to subject the treated fabricto a dry heat treatment at a temperature above 100 C. The fabric mayadvantageously be dried at temperatures in the range 60100 C. prior tothe heat treatment, which is preferably carried out at temperatures inthe range l25-250 C. Said heat treatment may be accomplished by any ofseveral known methods, for example by heating in a drying chamber, byironing the fabric, or by treating it with dry superheated steam.

For the preparation of compounds of Formula II, I prefer to employ2-amino-l-naphthalenesulfonic acid (Tobias acid) as a coupling componentwith the diazonium salt of the appropriate 6-amino-2-Y-ben z-X-azole. Itis well known that coupling occurs in the 1-position of the Tobias acidwith concomitant loss of the sulfonic acid group. Of course, the sameamino-azo coupling product will result when 2-aminonaphthalene isemployed as a coupling component, but the latter compound is todayconsidered a health hazard and is usually avoided.

A preferred mode of using and marketing those compounds of Formula Iwhich bear carboxy or sulfo substituents is by incorporating them intosolid or liquid soaps or detergents in an appropriate concentration, forexample 0.01 to 0.05 percent by weight of the whitening and brighteningagent. Said compounds are advantageously employed in their alkali metalor ammonium salt forms which are conveniently prepared from thecorresponding free acids by the interaction of the latter with alkalimetal or ammonium hydroxides. Irr acid form, these compounds have littleor no solubility in water, and in general they are most readilyutilizable as dispersions in aqueous media. The treatment of textilefabrics with these compounds is readily carried out by procedures whichare conventional in the art. For example, an aqueous dispersioncontaining about 0.0001 to about 0.5 percent by weight of the compoundand one or more suitable dispersing agents, for instance soap or anorganic sulfonate or sulfate, is applied to the fabric, which absorbsthe fluorescent compound and is whitened or brightened beneficiallythereby. This application of the compound can be conveniently carriedout in conjunction with either a rinsing or a washing operation.

The dispersions are readily formed, for example, by dissolving thecompound in a suitable solvent such as N,N-dimethylformamide,Z-ethoxyethanol, or glacial acetic acid and mixing the solution thusobtained in desired quantity with an aqueous soap or detergent solution.Those compounds of Formula I bearing carboxy or sulfo substituents onthe naphthotriazole ring are more readily dispersed in this manner thanare those not hearing such substituents, but the latter group ofcompounds can also be applied in dispersions as described above.

The compounds of Formula I which bear sulfo or carboxy groups on thenaphthalene ring thereof are prepared by coupling the above-describeddiazonium salt of 6-amino-2-Y-benz-X-azole with a carboxyorsulfo-substituted aminonaphthalene. The resulting amino-azo compoundsare oxidized in the above-described manner to produce benzoxazolyl-,benzothiazolyl-, and benzimidazolylnaphtho[l,2-d]triazoles substitutedwith one or two sulfonic or carboxylic acid groups substituted in thenaphthalene ring thereof. Among those aminonaphthalenes of particularvalue for said coupling reactions are S-amino-l-naphthalene sulfonicacid (Laurents acid), 6 amino-2-naphthalenesulfonic acid (Broennersacid), 6- amino 1,3 naphthalenedisulfonic acid, 7-amino-l,3-

naphthalenedisulfonic acid, 3 amino 2,7-naphthalenedisulfonic acid, 1amino-4,S-naphthalenedisulfonic acid, 2-amino-4,S-naphthalenedisulfonicacid, naphthionic acid, 2-amino-3-naphthoic acid, and the like.

For incorporation into detergents, I particularly prefer those compoundsof Formula I bearing a sulfo substituent in the 5-position of the2H-naphtho[l,2-d]ring, i.e., compounds having the structure of FormulaIII OaH Formula III wherein X and Y are defined above. These preferredspecies are not only highly substantive to natural and synthetic fiberswhen applied in aqueous solutions or dispersions, but they also have theadvantage of being derived from the relatively inexpensive couplingmaterial, naphthionic acid. Moreover, repeated application of thesepreferred compounds to white fabrics of natural and synthetic fibersresults in an enhancement of the whitening effect without thedevelopment of an undesirable color.

The required intermediate 6-amino-2-Y-benzo-X'-azole compounds ofFormula IV,

Formula IV wherein Y is defined above and X is O, S, or NH, are membersof a general class known in the art. They are readily prepared byreducing the corresponding 6-nitro-2- Y-benz-X'-azoles, which in turn,are prepared by interacting a carboxylic acid YCOOH, carboxylic acidester, YCOO-lower alkyl, or carboxylic acid chloride, YCOCl, withS-nitro-Z-aminophenol, S-nitro-Z-aminothiophenol or4-nitro-1,2-phenylenediamine, whereupon there is formed, respectively,6-nitro-2-Y-benzoxazole, 6- nitro-2-Y-benzothiazole or6-nitro-2-Y-benzimidazole.

The Y substituent and/ or the benzo ring of the intermediate in FormulaIV above can 'bear substituents which are chemically inert to otherfunctional groups in the molecule without deleterious elfects on thevalue of the resulting brightener compound. Indeed, I have found thatcertain substituents, for example alkoxy (e.g., methoxy, ethoxy and thelike), lower alkyl (e.g., methyl, isobutyl and the like), halo (e.g.,fluoro, chloro and bromo), sulfo, cyano, carboxy, and carbalkoxy groupshave the beneficial effect of slightly increasing the emissionwavelength of the substituted compound in comparison with the analogousunsubstituted compound. Thus, I envision compounds of Formula I whereinthe Y func tion bears substituents, particularly on the aromatic ring orrings thereof, as the full equivalents of the corresponding compoundsherein claimed which are not so substituted.

The intermediate amino-azo compounds prepared by coupling diazotized6-amino-2-Y-benz-X'-azole compounds to amino-substituted naphthalenes,that is compounds of Formulas V and VI,

Formula V N Y-o Formula VI wherein X, Y and Z as defined hereinabove,are new compounds. They are highly-colored pigments ranging in colorfrom orange through red and brown. These compounds are useful aspigments independently of their usefulness as intermediates herein. Theycan be employed for the various purposes for which azo pigments as aclass are well known.

The structures of the new compounds of my invention were determined bytheir mode of synthesis and by the correspondence of calculated andfound values of elemental analyses of representative samples, and werecorroborated by ultraviolet and infrared spectral analysis.

My invention is further illustrated by the following examples, without,however, being limited thereto.

EXAMPLE 1 I (A) 6-amino-2-styrylbenzoxazole (3.5 g., 0.015 mole) wasdissolved in 17 ml. of glacial acetic acid at 70 C., the solution wascooled to 30 C., and 18 ml. of 6 N hydrochloric acid was added. The finesuspension of the hydrochloride salt was cooled to C., and to it wasadded rapidly 11 ml. of percent aqueous sodium nitrite solution. Theresulting diazonium salt was soluble; a trace of insoluble material wasremoved by filtration, and the clear solution, along with 100 ml. of a20 percent aqueous solution of sodium acetate, was added to 5 g. of2-aminonaphthalene-6-sulfonic acid in 100 ml. of water at -20 C. Whenthe addition was complete, the pH of the mixture was 4.0 and it gave anegative diazonium test with R salt (the sodium salt of Z-naphthol-3,6-disulfonic acid). The pH was adjusted to 8.2 with 15 percent aqueoussodium hydroxide, and the mixture was heated to 90 C. The orangeproduct, consisting of 2-amino-l-(Z-styrylbenzoxazole 6yl)-azonaphthalene- 6-sulfonic acid in the form of its sodium salt, wascollected on a filter and washed with water.

(B) The entire yield of part A above (19 g.) was dissolved in a mixtureof 54 ml. of pyridine and 19 ml. of water heated at reflux. Maintainingthe solution at reflux, a solution containing 16.0 g. of copper sulfatepentahydrate in 50 m1. of pyridine and 16 ml. of water was added. Whenthe mixture had refluxed for 15 minutes, the color of the azo dye haddisappeared; reflux was continued for a total of two hours. The reactionmixture was poured into 600 ml. of water containing 140 ml. ofconcentrated hydrochloric acid. The resulting precipitate, consisting ofZ-(Z-styryI-benzoxazol 6 yl)-2H-naphtho- [1,2-d]triazole-7-sulfonicacid, was collected on a filter and washed with 5 percent sodiumchloride solution until the filtrate was colorless. The product waspurified first by suspending the filter cake in 200 ml. of watercontaining 5 g. of sodium carbonate and adding 1 g. of sodiumhydrosulfite. It was then recrystallized twice from boilingdimethylformamide, the second time with the aid of decolorizingcharcoal. Pure 2-(2-styrylbenzoxazol-6yl)-2H-naphtho[l,2-d]triazole-7-sulfonic acid thus prepared did not melt at300 C. Its chemical analysis agreed with the calculated values for amonohydrate. This compound corresponds to Formula I wherein Y is styryl,Z is 7-SO H, and X is 0.

Spectral analysis of this product showed that the compound had a maximumemission at 425 millimicrons and that maximum excitation was obtained at373 millimicrons.

EXAMPLE 2 (A) 2-styrylbenzoxazolyl 6 diazonium chloride was prepared asin Example 1(A) from 3.5 g. of 6-amino-2 styrylbenzoxazole. When thiscompound was coupled with sodium naphthionate (sodium1-amino-4-naphthalenesulfonate) there was obtained1-amino-2-(2-styrylbenzoxazol-6-yl)azonaphthalenel-sulfonic acid in theform of its sodium salt.

(B) The above-named amino-azo compound was oxidized according to theprocedure of Example 1(B). The resulting naphthotriazole compound wasdecolorized with sodium hydrosulfite and was recrystallized from aqueousdimethylformamide to give 2-(2-styrylbenzoxazol-6-yl)-2I-lT-naphtho[l,2-d]triazole-5-sulfonic acid as a yellow powder whichremained unmelted at 300 C. This compound corresponds to Formula Iwherein Y is styryl, Z is 5-SO H and X is 0. Spectral analysis of thisproduct showed a maximum emission at 426 millimicrons and a maximumexcitation at 374 millimicrons.

EXAMPLE 3 (A) 2-styrylbenzoxazolyl-6-diazonium chloride was prepared asin Example 1(A) from 1.18 g. (0.005 mole) of6-amino-2-styrylbenzoxazole. When this compound was coupled with Tobiasacid (2-amino-l-naphthalenesulfonic acid) there was obtained2-amino-l-(2-styrylbenzoxazol- 6-yl)-azonaphthalene as an orange-redprecipitate with melted at l96206 C. with decomposition.

(B) The above-named amino-azo compound was oxidized according to theprocedure of Example 1(B) to obtained2-(2-styry1benzoxazol-6-yl)-2I-I-naphthol[1,2-d] triazole, which melted,after recrystallization from 2- ethoxyethanol, at 218-220 C. Thiscompound corresponds to Formula I wherein Y is styryl, Z is H and X is0.

Spectral analysis of this product showed a maximum emission at 427millimicrons and a maximum excitation at 382 millimicrons.

EXAMPLE 4 Following the procedure given in Example 1(A), dia-zotized6-amino-2-styrylbenzoxazole was coupled with 2-amino-7-naphthalenesulfonic acid to give 2-arnino-1-(2-styrylbenzoxazol-6-yl)azouaphthalene-7-sulfonic acid as a scarletpigment. The amino-azo compound was oxidized in the manner described inExample 1(B) to obtain 2- (2-styrylbenzoxazol-6-yl) 2Hnaphtho[l,2-d]triazole- 8-sulfonic acid in the form of its sodium saltmonohydrate. The yellow powder remained unmelted at 360 C. This compoundcorresponds to Formula I wherein Y is styryl, Z is 8-SO H and X isoxygen.

Spectral analysis of this puroduct showed a maximum emission at 427millimicrons and a maximum excitation at 373 millimicrons.

EXAMPLE 5 Following the procedure given in Example 1A, diazotized6-amino-2-styrylbenzoxazole was coupled with 2-amino-S-naphthalenesulfonic acid to give 2-amino-l-(2- styrylbenzoxazol6 yl)azonaphthalene-S-sulfonic acid. The resulting amino-azo pigment wasoxidized in the manner described in Example 1(B) to obtain2-(2-styrylbenzoxazol-6-yl) 2H naphtho[1,2-d]triazole-6-sulfonic acid inthe form of a yellow powder which remained un- EXAMPLE 6 (A) One-tenthmole (22.4 g.) of stilbene-4-carboxylic acid was refluxed for two hourswith 0.45 mole (51.0 g.) of thionyl chloride to obtainstilbene-4-carboxylic acid chloride. The excess thionyl chloride wasstripped off under vacuum. Trichlorobenzene (500 ml.) was added and 100ml. of the solvent was then stripped off to remove the last traces ofthionyl chloride. The reaction mixture was cooled to 90 C. and 17.0 g.(0.11 mole) of 2- amino-S-nitrophenol and 8.7 g. (0.11 mole) of pyridinedissolved in 100 ml. of trichlorobenzene was added. The mixture-wasstirred at 140 C. for two hours, 1.0 g. of p-toluene-sulfonic acid wasadded, and 200 ml. of the solvent was distilled 01f to remove thepyridine. The remainder of the reaction mixture was refluxed overnight.When the solution was cooled, the product, 6-nitro-2-stilbylbenzoxazole,separated and was removed by filtration. Recrystallized from toluenewith the aid of decolorizing charcoal, pure 6-nitro-2-stilbylbenzoxazolewas obtained as yellow crystals melting at 237238 C.

(B) The nitro compound prepared in part A was reduced as follows: To asolution containing 5 mg. of stannous chloride and 1.3 ml. ofconcentrated hydrochloric acid in 600 ml. of 95 percent ethanol wasadded 12.0 g. (0.2 mole) of iron filings. The mixture was heated to theboiling point and there was added 17.1 g. (0.05 mole) of6-nitro-2-stilbylbenzoxazole in small portions. The reaction mixture wasallowed to reflux overnight. Since the resulting mixture containedinsoluble material, 300 ml. of Z-ethoxyethanol was added and thesolution was refluxed for an additional four hours. To the resultingclear solution was added 3.0 g. of sodium carbonate and 2.0 g. ofdibasic sodium phosphate. The mixture was then refluxed for ten minutes,decolorizing charcoal was added, and the solution was filtered hot. Thesolvent was stripped ed to a final volume of 250 ml. and the mixture waspoured into one liter of 5 percent sodium chloride solution. Theresulting yellow precipitate was removed by filtration and was washedwith water. The 6-amino 2-stilbylbenzoxazole thus obtained contained atrace of starting material as an impurity as observed by infraredspectral analysis. When the reduction was repeated as above, it wasfound that the nitro compound had been completely reduced.Recrystallized from butanol, the pure 6-amino-2-stilbylbenzoxazole thusprepared melted at 240-241 C.

(C) Following the procedure given in Example 1(A) but using 6.24 g.(0.02 mole) of 6-amino-2-stilbylbenzoxazole in place of the6-amino-2-styrylbenzoxazole therein, there was obtained2-stilbylbenzoxazole-6-yl diazonium chloride which was coupled with2-aminonaphthalene-1- sulfonic acid to obtain2-amino-1-(2-stilbylbenzoxazol-6- yl)azonaphthalene as a red pigmentmelting at 187 C.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain 2(2-stilbylbenzoxazol-6-yl)-2H-naphtho[1,2-d] triazole as a yellow powdermelting at 272-276 C. This compound corresponds to Formula I wherein Xis O, Y is 4-stilbyl and Z is H.

Spectral analysis of this product showed a maximum emission at 431millimicrons and a maximum excitation at 376 millimicrons.

EXAMPLE 7 (A) The procedure given in Example 6 was repeated with theexception that 2-stilbylbenzoxazol-6-yl diazonium chloride was coupledwith naphthionic acid to obtain 1- amino2-(2-stilbylbenzoxazol-6-yl)azonaphthalene-4-sulfonic acid in the formof its sodium salt as a red pigment.

(B) Following the procedure given in Example 1(B),

the above-named amino-azo compound was oxidized to obtain 2 (2stilbylbenz0xazol-6-yl)-2H-naphtho[1,2-d] triazole-S-sulfonic acid inthe form of its sodium salt monohydrate. This compound corresponds toFormula I wherein X is O, Y is 4-stilbyl and Z is 5-SO H.

Spectral analysis of this compound showed a maximum emission at 433millimicrons and a maximum excitation at 377 millimicrons.

EXAMPLE 8 (A) Following the procedure given in Example 6(A) with theexception that fl-naphthoic acid was employed instead ofstilbene-4-carboxylic acid, there was obtained2-(fl-naphthyl)-6-nitrobenzoxazole, which when recrystallized fromchlorobenzene melted at 215216 C.

(B) To a refluxing mixture containing 15.0 g. (0.25 mole) of ironfilings in 400 ml. of 70 percent aqueous acetic acid was added 14.5 g.(0.05 mole) of Z-(p-naphthyl)-6-nitrobenzoxazole (part A above). Themixture was refluxed for 2.25 hours. It was then filtered and thefiltrate was diluted with water. The product was collected on a filterand was recrystallized from 60 percent aqueous methanol with the aid ofdecolorizing charcoal to obtain 2-( 3-naphthyl-G-aminobenzoxazole) whichmelted at 180 C.

(C) Following the general procedure given in Example 1(A),2-(fi-naphthyl)-6-aminobenzoxazole was diazotized and coupled withnaphthionic acid to give 1-amino2-[2- (pnaphthyl)benzoxazol-6-yl]azonaphthalene-4-sulfonic acid in the form ofits sodium salt.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo pigment was oxidized to give 2- [H-fl-naphthyl)benzoxazol-G-yl] -2H-naphtho[ 1,2-d] triazole-S-sulfonic acid in theform of its sodium salt mono hydrate. The pale yellow powder remainedunmelted at 360 C. This compound corresponds to Formula I wherein X isO, Y is B-naphthyl and Z is S-SO H.

Spectral analysis of this compound showed a maximum emission at 413millimicrons and a maximum excitation at 363 millimicrons.

EXAMPLE 9 (A) 2-(B-naphthyl)benzoxazol-6-yl diazonium chloride preparedas in Example 8(C) was coupled with Tobias acid to obtain2-amino-l-[2(fl-naphthyl)benzoxazol-6-yl1azonaphthalene as a red pigmentmelting at 173- 176 C.

(B) The above-named amino-azo compound was oxidized in the mannerdescribed in Example 1(B) to obtain 2 [2(3 naphthyl)benzoxazol 6yl]naphtho[1,2-d] triazole which melted at 264-265 C. This compoundcorresponds to Formula I wherein X is O, Y is fl-naphthyl and Z is H.

Spectral analysis of this product showed a maximum emission at 411millimicrons and a maximum excitation at 361 millimicrons.

EXAMPLE 10 (A) Following the procedure given in Example 6(A),4-methylcinnamic acid was converted to the corresponding acid chloridewhich in turn was interacted with 2-amino-5-nitrophenol to give2-(4-methylstyryl-6-nitrobenzoxazole as yellow crystals which, afterrecrystallization from xylene, melted at 82183 C.

(B) The 2-(4-methylstyryl)-6-nitrobenzoxazole prepared in part A (13.7g.; 0.05 mole) was reduced by refluxing an alcoholic solution of thecompound with 11.5 g. of iron filings and 2.5 ml. of concentratedhydrochloric acid containing a trace of stannous chloride, according tothe general procedure given in Example 6(B). The resulting yellowcrystals, consisting of 2-(4-methylstyryl)- 6-aminobenzoxazole, meltedat 192192.5 C.

(C) Following the procedure given in Example 6(C),2-(4-methylstyryl)-6-aminobenzoxazole was diazotized and coupled with2-aminonaphthalene-1-sulfonic acid 11 Tobias acid) to give2-amino-l-[2(4-methylstyryl)benzoxazol-6-yl]azonaphthalene as a dark redpigment.

(D) Following the procedure given in Example 6(D), the above-namedamino-azo compound was oxidized to obtain 2-[2(4-methylstyryl)benzoxazol-G-yl]-2H-naphtho[1,2-d]triazole as a yellowpowder melting at 235- 236 C. This compound corresponds to Formula Iwherein X is O, Y is 4-methylstyryl and Z is H.

Spectral analysis of this product showed a maximum emission at 430millimicrons and a maximum excitation of 375 millimicrons.

EXAMPLE 11 (A) Following the procedure given in Example 1(A),2-(4-methylstyryl)-6-aminobenzoxazole (Example (B) was diazotized andcoupled with naphthionic acid to give 1- amino 2 [2(4methylstyryl)benzoxazol-G-yl]azonaphthalene-4-sulfonic acid in the formof its sodium salt as a scarlet pigment.

(B) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain2-[2(4-methylstyryl)benzoxazol-6-yl]-2H-naphtho-[l,2-d]triazole-5-sulfonic acid in the form of its sodium saltmonohydrate. The pale yellow powder remained unmelted at 300 C. Thiscompound corresponds to Formula I wherein X is O, Y is 4-methylstyryland Z is 5-SO -H.

Spectral analysis of this product showed a maximum emission at 430millimicrons and a maximum excitation at 374 millimicrons.

EXAMPLE 12 (A) Following the procedure given in Example 6(A),coumarin-3-carboxylic acid was converted to the corresponding acidchloride which in turn was interacted with 2-amino-5-nitrophenol toobtain 2-(3-coumarinyl)'6- nitrobenzoxazole which melted at 298-300 C.

(B) Following the procedure given in Example 8(B),2-(3-coumarinyl)-6-nitrobenzoxazole was reduced with iron and 70 percentaqueous acetic acid to obtain 2-(3- coumarinyl)-6-aminobenzoxazole whichmelted at 250- 270 C.

(C) Following the procedure given in Example 1(A), 2 (3 coumarinyl)6-aminobenzoxazole was diazotized and coupled withZ-aminonaphthalene-l-sulfonic acid (Tobias acid) to obtain2-amino-1-[2(3-coumarinyl) benzoxazol-6-yl] azonaphthalene.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain2-[2-(3-coumarinyl)benzoxazol-6-yl]-2H-naphtho- [1,2-d1triazole. Thiscompound corresponds to Formula I wherein X is O, Y is 3-coumarinyl, andZ is H.

EXAMPLE 13 (A) Polyphosphoric acid (360 g.) was heated to 60 C. and toit was added 98 g. (1 mole) of maleic anhydride. While stirring wasmaintained, 54.5 g. (0.05 mole) of orthoaminophenol was added, and themixture was heated rapidly to 155 C. After the mixture had been heatedfor four hours it was drowned in 2 liters of cold water. The resultingprecipitate was collected on a filter and washed with 5 percent sodiumchloride solution until free of acid. The 3(-benzoxazol-2-yl)acrylicacid thus prepared was purified by dissolving it in sodium carbonatesolution, filtering the solution and reprecipitating the free acid. Theproduct melted at 218-225 C. The 3-(benzoxazol-2- yl)acrylic acid (65g.) was then condensed with 49.3 g. of 5-nitro2-aminophenol in 400 g. ofpolyphosphoric acid as above. The resulting2-[2-(benzoxazol-2-yl)vinyl]-6- nitrobenzoxazole melted at 246248 C.

(B) The 2 [2 (benzoxazol-2-yl)vinyl]-6-nitrobenzoxazole was reduced withiron and hydrochloric acid in refluxing ethanol according to theprocedure described in Example 6(B) to obtain 2-[2-(benzoxazol-2-yl)vinyl]- 12 6-aminobenzoxazole at 272-278 C., afterrecrystallization from 2-ethoxyethanol.

(C) Following the procedure given in Example 1(A),2-[2-(benzoxazol-2-yl)vinyl1-6-aminobenzoxazole was diazotized andcoupled with naphthionic acid to obtain 1 amino 2[2-(2-benzoxazol-2-yl]vinyl)benzoxazol-6- yl]azonaphthalene-4-sulfonicacid in the form' of its sodium salt as dark brown-red pigment.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain 2 [2 ([benzoxazol 2yl)benzoxazol-6-yl]-2H naphtho[l,2-d]triazole-5-sulfonic acid in theform of its sodium salt monohydrate. This compound corresponds toFormula I wherein X is O, Y is 2-(benzoxazol-2-yl)vinyl and Z is 5-SO H.

EXAMPLE 14 (A) Following the procedure given in Example 6(A),benzofuran-Z-carboxylic acid was converted to the corresponding acidchloride and condensed with 2-amino-5 nitrophenol to give2-(benzofuran-2-yl)-6-nitrobenzoxazole which melted at 230-231" C.

(B) Following the general procedure given in Example 6(B),Z-(benzofuran-Z-yl)-6-nitrobenzoxazole was reduced with iron filings andhydrochloric acid in 50 percent 2-ethoxyethanol to obtain2-(benzofuran-2-yl)-6- aminobenzoxazole which, followingrecrystallization from 2-ethoxyethanol, melted at 245-246 C.

(C) Following the general procedure given in Example 1(A),Z-(benzofuran-Z-yl)-6-aminobenzoxazole was diazotized and coupled with2-aminonaphthalene-l-sulfonic acid (Tobias acid) to obtain2-amino-l-[2-(benzofuran-2- yl)benzoxazol-6-yl]azonaphthalene whichmelted at 220- 222 C.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain 2[2-(benzofuran-2-yl)benzoxazol 6 yl] 2H- naphtho[1,2-d]triazole as ayellow powder which melted at 250-251 C. after recrystallization frompyridine. This compound corresponds to Formula I wherein X is O, Y is2-benzofuranyl and Z is H.

EXAMPLE 15 (A) Following the general procedure given in Example 6(A),33.3 g. (0.2 mole) of cinnamoyl chloride was interacted with4-nitro-1,2-phenylenediamine to give 6-nitro- 2-styrylbenzimidazole,which melted at l05-l20 C. This material was not further purified, butrather was used directly for the next step.

(B) The above-mentioned 6-nitro-2-styrylbenzimidazole was reduced withstannous chloride and concentrated hydrochloric acid in refluxing2-ethoxyethanol to give 6- arnino-2-styrylbenzimidazole, which melted atl91193 C. after recrystallization from 95 percent ethanol.

(C) Following the procedure given in Example 1(A),6-amino-2-styrylbenzimidazole was diazotized and coupled with Tobiasacid to obtain 2-amino-1-(2-styrylbenzimidazol-6-yl)azonaphthalene as adull red pigment.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound was oxidized to obtain2-(2-styrylbenzirnidazol-6yl)-2H-naphthol[1,2-d] triazole as a yellowpowder melting at l84-194 C. with decomposition. This compoundcorresponds to Formula I wherein X is NH, Y is styryl and Z is H.

Spectral analysis of this product showed a maximum emission at 427millimicrons and a maximum excitation at 373 millimicrons.

EXAMPLE 16 When 2 (2-styrylbenzimidazol-6-yl)-2H-naphtho[l,2 d]triazoleof Example 15 is interacted with an equimolecular quantity ofethylenechlorohydrin in refluxing methoxyethanol in the presence of a.stoichiometric quantity of 50 percent aqueous sodium hydroxide solutionthere is obtained 2-[l-(2-hydroxyethyl)-2-styrylbenzimidazol-6-yl]-2H-naphthol[1,2-d1triazole. This compound corresponds to Formula Iwherein X is N-CHz-CHzOH Y is styryl and Z is H.

EXAMPLE 17 When 2-(2-styrylbenzimidazol-6-yl) -2H-naphtho[ 1,2-d]triazole of Example is interacted with an equimolecular quantity ofallyl chloride in refluxing methoxyethanol in the presence of astoichiometric quantity of 50 percent aqueous sodium hydroxide solutionthere is obtained 2- (l-allyl-2-styrylbenzimidiazol-G-yl) 2H naphtho[1,2-d] triazole. This compound corresponds to Formula I wherein X isEXAMPLE 18 When 2- 2-styrylbenzimidazol-6-yl -2H-naphtho 1,2-d] triazoleof Example 15 is interacted with an equimolecular quantity ofacrylonitrile in Z-ethoxyethanol at about 50 C. in the presence of astoichiometric quantity of 50 percent aqueous sodium hydroxide solutionand a trace of cuprous chloride to retard polymerization of theacrylonitrile, there is obtained2-[1-(2-cyanoethyl)-2-styrylbenzirnidazol-6-yl]-2H-naphthol[l,2-d]triazole. This compound corresponds to Formula I wherein X is Y isstyryl and Z is Similarly, when 2-(2-styrylbenzimidazol-6-yl)-2H-naphtho[ l,2-d]triazole is interacted with the following reagents, theindicated products of my invention are produced:

Reagent Product Styrene oxide 2-[1-(2-phenyl-2-hydroxyethyl)-2-styrylbenzimidazol-d-yll-ZH-naphtho- [1,2-d1triaz0le.

Methyl lodide 2-(l-methyl-2-styrylbenzimldazol6-yl)-2H-naphtho[1,2-d]triazole.

Ethyl bromide 2-(1-ethyl-2-styrylbenzimidazol-6-yl)-2H-naphtho[l,2-d-]triazole.

e-(lhloroaeetlc aeid 2-(1-carboxymethyl-2-styrylbenzlmldazol-S-yl)-2H-naphtho[1,2-d]triazole. Ethyl B-chloropropio-2-[l-(B-carbethoxyethyl)-2-styrylbenzimldazol- Methallyl chloride2-(1-methallyl-2-styrylbenzimidazol-o-yl)- 2-hydroxy-3F(2-hy-2-[1-(2-hydroxy-3-[2-hydroxyethoxyl-propyl hydroxyethoxy)Z-styrylbenzimidazol-6-yl]-2H-naphthopropyl chloride. [l,2-d]triazole.

2,3dihydroxypropy1 2-[1-(2,3-dihydroxypropyl)-2-styrylbenzlmldachloride.zol-6-yl1-2H-naphtho[1,2-d]triazole.

Benzyl chloride 2-(l-benzyl-2-styrylbenzimidazol6-yl)-2H-naphtho[l,2-d]triazole. Phenethyl bromlde.2-(l-phenethyl-Zstyrylbenzimidazol-oyl)- 2H-naphtho[l,2-d]ttiazole.2-[l-(p-methoxybenzyl)-2-styrylbenzlmldazolp-Methoxybenzyl chloride.6-yl1-2H-naphtholl,2-dltriazole.

EXAMPLE 19 EMMPLE 20 (A) Dibenzofuran-Z-carboxylic acid (5.25 g.; 0.025mole) was converted to its acid chloride and the latter compound wasinteracted with an equimolecular quantity of Z-amino-S-nitrophenolaccording to the [procedure given in Example 6(A) to obtain2-(dibenzofuran-2-yl)-6-nitrobenzoxazole which melted at 231232 C. afterrecrystallization from trichlorobenzene.

(B) Following the procedure given in Example 6(3), 2-(dibenzofuran-Z-yl)-6-nitrobenzoxazole is reduced to obtain2-(dibenzofuran-Z-yl)-6-arninobenzoxazole.

(C) By diazotization and coupling of 2-(dibenzofuran-2-yl)-6-aminobenzoxazole with 2-aminonaphthalene-1-sulfonic acidaccording to the foregoing procedures there is obtained 2-amino-l-[2(dibenzofuran-Z-yl)benzoxazol-6- yl] azonaphthalene.

(D) Oxidation of the above-named amino-azo compound according to theforegoing procedures yields 2-[2- (dibenzofuran-Z-yl)benzoxazol-G-yl]ZH-naphtho [1,2-d] triazole. This compound corresponds to Formula Iwherein X is O, Y is dibenzofuran-Z-yl, and Z is H.

EXAMPLE 21 (A) Following the procedure given in Example 1 (A), cinnamoylchloride is interacted with 2-amino-5-nitrothim phenol to obtain2-styryl-6-nitrobenzothiazole.

(B) Reduction of the Z-styryl-G-nitrobenzothiazole of part A by means ofiron filings and acetic acid in accordance with the procedure given inExample 8(B) yields 2-styryl-6-aminobenzothiazole.

(C) Following the procedure given in Example 1(A), diazotization of2-styryl-6-aminobenzothiazole and coupling of the resulting diazoniumchloride with Tobias acid, there is obtained 2amino-1-(2-styrylbenzothiazol-6-yl) azonaphthalene.

(D) Following the procedure given in Example 1(B), the above-namedamino-azo compound is oxidized to obtain 2-(2-styrylbenzothiazol-6-yl)2H benzo[1,2-d]triazole. This compound correspondings to Formula Iwherein X is S, Y is styryl, and Z is H.

EXAMPLE 22.

(A) When 2-styryl-G-aminobenzothiazole of Example 21 (B) is diazotizedas described in Example 1(A) and coupled with naphthionic acid, there isobtained l-amino-Z- (2-styrylbenzothiazol-6-yl)-azonaphthalene 4sulfonic acid.

(B) Oxidation of the above-named amino-azo compound according to theprocedure given in Example 1(B) yields 2(Z-styrylbenzothiazol-G-yl)-2H-naphtho[1,2-d] triazole-S-sulfonic acid,which is conveniently used in the form of its sodium salt. This compoundcorresponds to Formula I wherein X is S, Y is styryl and Z is 5-SO H.

EXAMPLE 23 (A) Following the general procedure given in Example 1(A),diazotized 2-styryl-6-aminobcnzoxazole is coupled with2-arnino-3-naphthoic acid to obtain 2-amino-1-(2-styrylbenzoaxazol-6-yl)-azonaphthalene-3-carboxylic acid.

(B) Oxidation of the above-named amino-azo compound according to theprocedure given in Example 1(B) yields 2(2-styrylbenzoxazol-6-yl)-2H-naphtho[1,2-d]triazole-4-carboxylic acid.This compound corresponds to Formula I wherein X=O, Y=styryl andZ=4-COOI-L To further exemplify my invention, there may also be preparedaccording to the procedures illustrated above, the following amino-awcompounds of my invention. The starting materials and processes forpreparing these pigments will be obvious to one skilled in the art inview of the foregoing disclosure.

2-amino-1-[2- (4-phenyl-l,3-butadienyl)benzoxazol-6- yl] azonaphthalene2-amino-1- [2- (9-phenanthryl) benzoxazol-6-yl] azonaphthlene-G-sulfonicacidZ-aminol-[2-(2-indenyl)benzothiazol-6-yl]azonaphthalene-3-carboxylicacid l-amino-l-[2-(3-quinolinyl)benzothiazol-6-yl]azonaphthalene-4sulfonic acid1-amino-2-[2-(4-[Z-fiuryl]-1,3-butadienyl)benzothiazol- 6-yl]azonaphthalene-4-sulfonic acid 1-amino-2- [2- 9-fluorenylidenylmethyl)benzoxazol-6-yl] azonaphthalene-4,5-dicarboxylic acid2-amino-1-[2-(2-[2-benzofuranyl]vinyl)benzimidazol-6- yl]azonaphthalene-3,6-disulfonic acid2-amino-1-[2-(6-methoxybenzofuran-2-yl)benzimidazol-6-yl]azonaphthalene-6-sulfonic acid l-amino-Z- [2- (2- B-naphthyl]vinyl) benzothiazol-G-yl] azonaphthalene-4-sulfonic acid2-amino-1-[2-(2- [,B-naphthyl] vinyl benzoxazol-6-yl] azonaphthaleneZ-amino- 1- [2- (2- [a-naphthyl] vinyl) benzoxazol-G-yl] azonaphthalenel-amino-2-[2-(3-methoxy-2-naphthyl)benzoxazol-6-yl]azonaphthalene-4-sulfonic acid Z-amino-l [2-(3-methoxy-2-naphthyl)benzoxazol-6-yl1- azonaphthaleneZ-amino-l-[2-(4-phenylstyryl)benzoxazol-6-yl1azonaphthalene1-amino-2-[2-(4-phenylstyryl)benzoxazol-6-yl1aw naphthalene-4-sulfonicacid Z-amino-l- [2-(2-indolyl)benzoxazol-6-yl] azona-phthalene1-amino-2-[2-(2-indolyl)benzoxazol-6-yl] azonaphthalene- 4-sulfonic acid2-amino-l-[2-(6-mcthoxybenzofuran-2-yl)benzoxazol-6- yl] azonaphthalene2-amino-1-[2-(6-methoxy-3-methylbenzofuran-2-yl)bcnzoxazol-fi-yl]azonaphthaleneZ-amino-l-[2-(2-[4-pyridyl]vinyl)benzoxazole-6-yl] azonaphthalenel-amino-Z-[2-(Z-[Z-pyridyl]vinyl)benzoxazol-6-yl]azonaphthalene-4-sulfonic acid1-amino-2-[2-(6-methyl-2-benzofuranyl)benzoimidazol- 6-yl]azonaphthalene-4-sulfonic acidZ-amino-l-(Z-styrylbenzoxazol-G-yl)azonaphthalene- '5,7-disulfonic acidBy oxidation of the foregoing amino-azo compounds according to theprocedure disclosed hereinabove there is obtained the followingnaphtho[1,2-d]triazole compounds of my invention:

2-[2-(4-phenyl-1,3-butadienyl)benzoxazol--yl] -2H- naphtho[ l,2-d]triazole 2- [2-(9-phenanthryl) benzoxazol-G-yl] -2H-naphtho 1,2-d]triazole-7-sulfonic acid2-[2-(2-indenyl)benzothiazol-6-yl]-2H-naphtho[1,2-d]

triazole-4-carboxylic acid 2-[2-(3-quinolinyl)benzothiazol-6-yl]-2H-naphtho 1,2-d] triazole-S-sulfonicacid 2- [2- (4-[2-furyl] -1,3-butadienyl) benzothiazol-6-yl]- ZH-naphtho1,2-d] triazole-S-snlfonic acid 2-[2-(9-fiuorenylidenylmethyl)benzoxazol-6-yl]-2H- naphtho 1,2-d]triazole-S ,G-dicarboxylic acid 2- [2-(2-[2-benzofuranyl] vinyl)beuzimidaml-6-yl1- 2H-naphtho[ l,2-d]triazlole-4,7-disulfonic acid 2-[2- (6-methoxybenzofuran-2-yl)benzimidazol-G-yl]- ZH-naphtho 1,2-d]triazole-7-sulfonic acid 2- [2-(2-[fl-naphthyl1vinyl)benzothiazol-6-yl1-2H- naphtho[ 1,2-d] triazole-S-sulfonic acid 2-[2-(2- [fl-naphthyl] vinyl) benzoxazol-6-yl1-2H- naphtho 1,2-d] triazole2-[2-(2-[u-naphthyl] vinyl)benzoxazol-6-yl]-2H- naphtho 1,2-d] triazole2-[2-(3-methoxy-2-naphthyl)benzoxazol-6-yl1-2H- naphthol,2-d]triazole--sulfonic acid2-[2-(3-methoxy-2-naphthyl)benzoxazol-G-yl] -2H- naphtho[ 1,2-d]triazole 2-[2- (4-phenylstyryl) benz0xazol-6-y11-2H-naphtho [1,2-d]triazole 2- [2-(4-phenylstyryl) benzoxazol-G-yl] -2H-naphtho [1,2-d]triazole-S-sulfonic acid2-[2-(2-indolyl)benzoxazol-6-yl]-2H-naphtho[1,2-d]

triazole 2-[2-(2-indolyl)benzoxazol-G-yl]-2H-naphtho[1,2-d]

triazole-S-sulfonic acid 2- [2-(6-methoxybenzofuran-2-yl)benzoxazol-6-yl1-2H- naphtho 1,2-d] triazole 2-[2-(6-methoxy-3-methylbenzofi1ran-2-yl)benzoxazol- 6-yl] -2Hnaphtho[1,2-d] triazole 2- [2- (2- [4-pyridyl] vinyl) benzoxazol-6-yl1-2H-naphtho 1,2-d]triazole 2-[2- (2- [2-pyridyl1vinyl) benzoxazol-6-yl1-2H-naphtho[ 1,2-d] triazole-S-sulfonic acid2-[2-(6-methyl-2-benzofuranyl)benzimidazol-6-yl1-2H- naphtho 1,2-d]triazole-S-sulfonic acid 2-(2-styrylbenzoxazol-6- l)-2H-naphtho[1,2-d]

triazole-6,8-disulfonic acid The effectiveness of the opticalbrightening agents prepared above is determined by a variety of tests.The tests include dyeings made on various fabrics. Such dyeings can beaccomplished by the subjecting cloth samples to launderings fromdetergent solutions containing optical brightening quantities of thecompounds. Another method previously described hereinabove is toimpregnate textile fibers from an aqueous dispersion followed by heattreating of the impregnated fibers. Still another method involves theincorporation of the compound to be tested into a polymeric melt. Ineach of these tests, the substrate treated with the optical brighteningagent is subjected to color comparison with untreated samples of thesame substrate. A color difference meter is used to measure differencesin shade and/or degree of whiteness between the samples. The followingprocedures are illustrative of these methods for determining theeifectiveness of the optical brightening agents of this invention.

EXAMPLE 24 A solution of 2 [2 (6 methoxybenzofuran-Z-yD-benzoxazol-S-yl]-2H-naphtho[1,2-d]triazole in dimethyl terephthalate wasprepared by intermixing 0.04 g. of the brightener with 10.00 g. ofdimethyl terephthalate and then melting the two solids together, withcontinual stirring and under a carbon dioxide atmosphere, by immersingthe container in a bath of diethyl phthalate which was then heated to200 C. during a period of about 15-20 minutes. The fluid mixture wasthen poured into a mortar and ground to a fine powder. The solidsolution of brightener in dimethyl terephthalate was incorporated intopolyethylene terephthalate by blending 1.0 g. of the brightenerdimethylterephthalate powder with 18.0 g. of predried polyethylene terephthalatechips and 1.0 g. of dimethyl terephthalate. The mixture was melted undera carbon dioxide atmosphere by immersing the container in a bath ofdiethyl phthalate at C. after which the bath was heated to boiling(295-7 C.). The melt was stirred for five minutes, and it then wasremoved from the bath and allowed to cool to room temperature,continually under carbon dioxide. The polyethylene terephthalate castingwas then broken up and ball milled with stoneware pellets in distilledwater. The particles were dried and screened, and those passing througha 40 mesh screen were packed into a 5 cm. polystyrene Petri dish. Thecolor of the sample was then measured on a color dilierence meter(Hunterlab Model D-25, Hunter Associates Laboratory, Mc- Lean, Va.) incomparison with a standard magnesium oxide plate. These values were thencompared with those for a blank sample prepared in the identical wayexcept that the optical brightener was omitted. The values of the blanksample were determined at the same time as those of the sample tested.Following are the readings obtained in comparison with the standardmagnesium oxide plate:

HUNTERLAB D-25 READINGS 17 These results show that the shade ofwhiteness imparted to the polyethylene terephthalate was in the pink andblue range considered most desirable in the textile art. For thesignificance of the values recorded above, see R. S. Hunter,Photoelectric Color Difference Meter, J. Opt. Soc. Am.. 48, 985 (1958).

EXAMPLE 25 The elfectiveness of the optical brightening agents ofFormula I which bear carboxy or sulfo substituents for brightening nylonfabric was determined by making dyeings from laundering solutionscontaining optical brightening quantities of the compounds. Thus, asolution containing 0.10 g. of the brightener compound to be tested inthe form of the sodium salt, in 100 ml. of N,N-dimethylformamide wasdiluted with water to 1000 ml. A Launder-Ometer (a standard laboratorywashing machine of the American Association of Textile Chemists andColorists, manufactured by Atlas Electric Devices, Chicago, 111., anddescribed in the Technical Manual and Year Book of the Association,Howes Publishing 00., Inc., New York, N.Y., vol. XXV-III, 1952, pp.82-83) container was charged with 10.0 ml. of the brightener solutionand 100.0 ml. of a 0.3 percent solution of an alkyl aryl sulfonatedetergent which initially contained no brightening agent. Then 90.0 ml.of tap water and one 5.0 gram swatch of nylon talfeta cloth was added tothe container. The Launder-Ometer was run for twenty minutes at 120 F.The cloth was removed, rinsed for two minutes in cold running tap waterand then ironed dry. The swatch was then measured for whiteness on areflectometer (Hunterlab Model D-40YZ Whiteness Reflectometer, HunterAssociates Laboratory, McLean, Va.) in accordance with the AmericanAssociation of Textile Chemists and Colorists Test Method 110-1968described in the Technical Manual of the American Association of TextileChemists and Colorists, vol. 45, pp.t;.96 and 97 (1969). Five readingswere made on each cloth and the average reading used to calculate thewhiteness value. The following table lists the whiteness values obtainedfor the compounds of Example 2, Example 7, and Example 1(B) above andfor the known compound, 2-(2-phenylbenzoxazol-G-yl) 2H-naphthol[l,2-d]triazole-S-sulfonic acid. Also shown is the whiteness value for nylonswatches laundered in the same detergent solution and in the same mannerdescribed above except that no brightener compound was added.

Hunterlab D-40YZ readings Nylon swatch laundered: Whiteness With nobrightener 69.0 In presence of 2 (2 phenylbenzoxazol-G-yl)2H-naphtho[1,2-d]triazole-5-sulfonic acid 76.2 In the presence of2-(2-styrylbenzoxazo1-6-yl) 2H naphtho[1,2-d1triazole-5-sulfonic acid(Example 2) 95.7 In the presence of 2-(2-stilbylbenzoxazol-6-yl) 2Hnaphtho[1,2-d]triazole-5-sulfonic acid (Example 7) 95.2 In the presenceof 2-(2-styryIbenzoxazol-6-yl) 2H n-aphtho[1,2-d]triazole-7-sulfonicacid (Example 1(B)) 95.4

These results show the unexpectedly high degree of whiteness imparted tonylon fabric by compounds of the type represented by Formula I in whichthe Y substituent contains four and seven carbon double bonds comparedto the degree of whiteness imparted by the known compound which containsthree double bonds in the correspodning substituent. For a detailedexplanation of the Hunterlab D-40YZ and the significance of thewhiteness values recorded above, see R. S. Hunter, New Reflect ometerand Its Use for Whiteness Measurementfl. Opt. Soc. Am., 50, 44 (1960).

18 EXAMPLE 26 A detergent composition containing an effective whiteningand brightening amount of 2-(2-styrylbenzoxazol-6-yl)-2H-naphtho[1,2-d]triazole-5-sulfonic acid was prepared as follows:

An accurately-weighed sample of 100.0 mg. of the brightener compound(Example 2) was placed in a mixing tube along with 10-20 granules ofsolid white detergent (consisting of sodium alkyl sulfates andsulfonates and a builder of sodium tripolyphosphate) and one ml. of 1 Nsodium hydroxide solution. The mixture was triturated for 30 secondswith a motor-driven pestle. Twenty grams of the solid white detergentand 17 ml. of water were then added and the mixture was triturated againfor one minute. The mixture was then placed in a Petri-dish and dried ina forced air oven at C. for two hours. The cake was broken up with aspatula, and the chunks were forced through a 20mesh sieve. The screenedmaterial was collected on a 60-mesh sieve and shaken to remove thefines. The resulting brightener-de tergent composition retained on the60-mesh screen was used for testing the composition in accordance withstandard tests employed in the brightener and detergent trades.

I claim:

1. A compound of the formula wherein X is a member of the classconsisting of O, S and N-R, where R is a member of the class consistingof H, lower alkyl, hydroxy-lower alkyl, hydroxy-oxaalkyl, phenyl-loweralkyl, cyano-lower alkyl,, carboxy-lower alkyl, carbo-lower alkoxy-loweralkyl, phenyl-hydroxylower alkyl, and lower alkenyl; Y is an organicradical selected from the class consisting of styryl, S-phenyl-Z- furyl,2-quinolinyl, 3-coumarinyl, Z-benzofuranyl, Z-dibenzofuranyl,3-dibenzofuranyl, p-phenylene-3-coumarinyl, Z-benzoxazolyl,2-(2-benzimidazoly1)vinyl, 4-stilbyl, 4-(2-furyl)-1,3-butadienyl,3-indolyl, 3-indanyl, 9-phenanthryl, Z-quinoxalinyl,4-(2-thienyl)-1,3-butadienyl, 2- (2 pyridyl)vinyl, 2-(4 pyridyDvinyl,2-(2 naphthyl) vinyl, 2-(1-naphthyl)vinyl, 4-pheny1-1,3-butadienyl, 2-(4-biphenylyl)vinyl, Z-naphthyl, 9 fluorenylidylmethyl, and l-indenyl;and Z is H, 1-2 carboxy or 1-2 sulfo groups.

2. A compound according to claim 1 of the formula wherein Y is a memberof the class consisting of styryl, 4-stilbyl, Z-benzofuranyl,2-(6-methoxybenzofuranyl), 2- (6-methoxy-3-methylbenzofuranyl),Z-(B-naphthyDvinyl, 2-(u-naphthyl)vinyl, 4-phenyl-l,3-butadienyl, 3coumarinyl, 9-phenanthryl, 3-quino1inyl, 3-methoxy-2-naphthyl and4-phenylstyryl and Z' is a member of the group consisting of H and SO H.

3. A compound according to claim 1 of the formula wherein X is a memberof the class consisting of O, S, and NR and Z' is a member of the classconsisting of H and SO H, wherein R is a member of the group consistingof H, lower alkyl, hydroxy-lower alkyl, hydroxy-oxaalkyl, phenyl-loweralkyl, cyano-lower alkyl, carboxy-lower alkyl, carbalkoxy-lower alkyl,phenyl hydroxy-lower alkyl, allyl, and methallyl.

4. A compound according to claim 1 of the formula 5. A compoundaccording to claim 1 of the formula N CMH 6. A compound according toclaim 1 of the formula wherein Z is a member of the group consisting ofH and SO H.

8. A compound according to claim 1 of the formula -cn=orr-c HOE 10. Acompound according to claim 1 of the formula wherein Z is a member ofthe group consisting of H and SO H.

References Cited UNITED STATES PATENTS 2,713,056 7/1953 Sartori 260-3043,575,956 4/1971 Crounse 260-157 3,689,425 9/1972 Crounse 252-117 0FOREIGN PATENTS 481,929 11/1969 Switzerland 260-240 D 1,456,745 9/1966France 260-240 D JOHN D. RANDOLPH, Primary Examiner US. Cl. X.R.

10620, 164, 176; 11733.5 R, 33.5 T, 138, 152; 252- 110, 117, 301.2 W,524, 531, 535, 539, 543; 260-37 NP,

0 78 R, 141, 157, 158, 240 C, 240 C A, 240 E, 240 R, 288 R,

304, 306.8 F, 307 D, 308 B, 309.2

Page 1 of 2 UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OFCORRECTION PATENT NO. I 3 03 135 DATED April 9, 1974 INVENTOR(S) 1Nathan N. Crounse It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 3, line 5, insert a comma after "carbomethoxymethyl".

Column 3, line 10, "h d should read hydroxypropyl Column 7, line 23, asshould read are Column 19, Claim 4, line 31, the part of the structurethat reads N should read N Page 2 of 2 UNITED STATES PATENT ANDTRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,803,135

DATED April 9, 1974 |NVENT0R(5) 3 Nathan N. Crounse It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 19, Claim 6, line 67, the part of the structure that reads shouldread Signed and Scaled this T wenty-fifih D3) of J ly 1978 [SEAL]Attest:

N RUT C. MASON DO ALD W BANNER Arresting Oflicer Commissioner of Patentsand Trademarks

